超临界CO2流体中分散染料溶解度研究进展

综述了超临界CO_2流体中染料溶解度的测试装置与方法。分析了超临界CO_2流体工艺参数与染料化学结构对分散染料溶解度的影响;总结了国内外近20年分散染料在超临界CO_2流体中溶解度数据,并介绍了分散染料在超临界CO_2中的溶解度增溶技术。指出加强染料结构对其溶解性能作用原理及影响规律剖析,超临界CO_2中染料溶解行为数据库构建、染料拼色与配色研究三方面为未来的研究重点。     

分散红343、分散蓝366及其混合物在超临界CO_2中的溶解度测定和关联

为超临界CO2染色工艺提供必要的基础数据,采用静态循环法在343.2～383.2 K,12～28 Mpa温度压力范围内,测定了分散红343和分散蓝366及其混合物在超临界CO2中的溶解度.实验结果表明,二元体系(分散红343+CO2,分散蓝366+CO2)和三元体系(分散红343+分散蓝366+CO2)中染料的溶解度均随温度和压力的升高而增大;染料分子的极性对其在超临界CO2中的溶解度影响较大;三元体系中两种染料的溶解存在"共溶剂效应"和竞争溶解作用;两种染料在二元和三元体系中的溶解度实验数据用Chrastil方程关联,结果较好.     

聚对苯二甲酸丁二酯纤维在超临界二氧化碳介质中的染色研究

用超临界二氧化碳作介质，在40～120℃，10～30MPa条件下使用分散染料对聚对苯二甲酸丁二酯(PBT)纤维进行染色试验，并测定了3种分散染料在超临界二氧化碳介质中的溶解度。研究了染色温度、压力、时间及染料结构对染料上染量的影响，考察了染料溶解度与染料上染量的关系。试验表明，在80℃，20MPa下，染色30min，PBT纤维能得到良好的染色效果，上染量达4．01mg/g(分散红60)、2．43mg／g(分散黄23)、11．19mg/g(分散蓝79)。     

超临界二氧化碳染色技术研究进展

概述了超临界二氧化碳染色技术的染色机理,对不同染料的染色工艺条件的研究情况做了分析。阐述了染料研究和混合染料拼色研究的进展情况。对超临界二氧化碳的染色热力学和动力学性研究情况做了论述,对染料在超临界二氧化碳中的溶解度、染料在纤维与超临界CO2间的分配规律、染料在纤维中的扩散行为做了分析论述。对染色设备的国内外进展情况做了分析论述。指出了超临界二氧化碳染色技术产业化应用应解决的关键问题是增强染料的溶解和在纤维中的扩散,以及高压操作下大容积染色釜的研制。     

超临界二氧化碳染色过程

针对传统水染工艺不能从根本上解决印染行业水环境污染严重及资源消耗、浪费大的问题，介绍了一种全新的清洁生产技术——超临界CO2染色过程，重点分析了超临界流体和超临界CO2染色工艺的特点，阐述了分散染料在超临界CO2中的溶解和扩散特性以及纤维表面结构及其改性在染色过程中的作用，提出了超临界CO2染色技术研究的若干观点。     

分散橙30和分散橙31在超临界CO2中的溶解度测定

超临界CO2染色技术是一种新型的无水染色技术,染料在超临界CO2中的溶解度是超临界CO2染色工艺的一个重要基础数据.在压力16～28 MPa、温度343.2～383.2 K范围内,采用静态循环法对分散橙30和分散橙31两种分散染料在超临界CO2中的溶解度进行了测定.两者的溶解度范围分别为2.1×10-5～7.8×10-5和1.4×10-5～3.7×10-5(摩尔分率),均随着压力的升高而升高.由溶解度随温度变化趋势推测,分散橙30在16 MPa附近将出现压力转折点,而分散橙31在实验范围内未出现转折压力.两种染料的溶解度数据比较表明,苯环上引入-Cl,可使溶解度明显提高.分散橙30和分散橙31的溶解度实验数据用Chrastil经验模型拟合,平均相对偏差分别为4.9%和2.46%.     

溢流法测定超临界CO_2在聚己酸内酯中的溶解

以超临界CO2作为溶剂,采用溢流法研究聚己酸内酯(PCL)在CO2中的溶胀过程和超临界CO2/PCL体系的热力学平衡规律。考察了温度、压力对溶解度的变化趋势,分析加入有机溶剂后对CO2在聚合物中的溶解度的影响,并应用P-T(Patel-Teja)方程作为热力学模型分析和计算溶解规律。结果表明:CO2的溶解度随温度升高而降低,随压力增大而增大,有机溶剂的加入能够进一步提高CO2的溶解度,在相同的温度压力条件下,加入相当于CO2质量的2.26%的二氯甲烷,最多可使溶解度增加28.06%。在温度313.15—353.15 K、压力10—20 MPa范围内,P-T方程能较好地预测CO2在PCL中的溶解度,其相对误差在-12.53%—12.01%。     

黏土对超临界CO2在聚乳酸中溶解性能的影响

采用体积法测量超临界CO2在聚乳酸(PLA)及PLA/黏土纳米复合材料中的溶解性能,研究黏土对超临界CO2在PLA中溶解速率和溶解度的影响.结果表明:黏土的存在使超临界CO2在PLA中的溶解速率大大降低,溶解度从纯PLA的12.7%降低到复合材料的5.1%(测试温度170℃、压力10MPa),降幅达60%.从材料的流变性能和结晶性能两方面分析其内在原因.     

超临界CO2流体萃取分离乙醛酸的研究

本文通过测定草酸和乙醛酸在不同的温度和压力下在超临界CO2流体中的溶解度，确定超临界CO2流体萃取乙醛酸的工艺条件。在一定的条件下证明利用该工艺的可行性，为进一步研究此方法分离乙醛酸奠定了基础。     

超临界CO_2中分散红54在涤纶织物中的扩散研究

超临界CO2染色技术是一种新型的绿色环保染色技术,超临界CO2中分散染料在涤纶织物中的扩散性能是超临界CO2染色技术的一个重要基础。为了研究超临界CO2中分散染料在涤纶织物中的扩散性能,研究采用"卷层法",在温度70~110℃,压力16~24 MPa下,选用分散红54在自行研制的超临界CO2染色装置中对涤纶织物进行超临界CO2染色扩散实验。实验结果表明,染料在涤纶织物中的扩散过程是一边上染纤维一边向纤维内部扩散的过程,所建立的染色—扩散模型成功地描述了这一过程。随着温度的升高,染色速率系数与扩散系数之比随之增大,随着压力的升高,两者之比先升后降。     

Relationship between the solubility of disperse dyes and the equilibrium dye adsorption in supercritical fluid dyeing

In order to understand the dyeing behaviour of synthetic fibres in supercritical carbon dioxide, the solubility of some disperse dyes in supercritical fluid, as well as the rate of dyeing and the equilibrium adsorption of these dyes, have been studied. Dye solubility was measured by a dynamic analytic method at a range of pressure (7.5–25 MPa) and temperature (50–145 °C). The apparent rate of dyeing was measured and the dyeing isotherm was obtained by plotting the equilibrium dye adsorption against the equilibrium dyebath concentration. Linear isotherms were obtained when poly(ethylene terephthalate) samples were dyed with the disperse dyes. The mechanism of dyeing using supercritical carbon dioxide was discussed by considering the solubility, the dyeing rate and the dyeing isotherm.     

Correlation of solubility data of azo disperse dyes with the dye uptake of poly(ethylene terephthalate) fibres in supercritical carbon dioxide

Solubility data of disperse azo dyes in supercritical carbon dioxide are presented for dyeings of poly(ethylene terephthalate) fibres with CI Disperse Red 167:1, carried out at 200–300 bar and 80–120 °C, with varying amounts of adulterants. The same dyeings were also carried out in water for comparison. Scanning electron micrographs were taken of the dyes which show a growth of dye crystals during treatment in supercritical carbon dioxide. The paper reports that at 120 °C, melting of the pure dye CI Disperse Red 167:1 is observed. The presence of adulterants in the dye formulations help prevent agglomeration by acting as spacers between the dye molecules. Dyeings of PETP carried out under conditions of the highest solubility of the dye in supercritical carbon dioxide do not necessarily result in a very high dye uptake. This was shown by pressure- and temperature-dependent dyeing experiments of PETP in supercritical carbon dioxide.     

超临界二氧化碳流体染色工程化研究进展

介绍了超临界CO2流体基本性质;综述了近年来国内外在超临界CO2流体工程化染色装备系统、工程化染色工艺技术和专用染料三方面的最新研究进展。结果表明:经过多年发展,适用于散纤维、筒纱、织物的超临界CO2流体工程化染色装备开始逐步推向市场,并可通过智能安全联锁系统保障装备的安全运行;聚酯纤维材料超临界CO2流体染色工程化染色工艺技术日趋成熟,已经在世界范围内进行了初步生产应用;但天然纤维超临界CO2流体染色专用染料仍存在色牢度差,易于造成设备腐蚀等问题。指出超临界CO2流体染色专用商品化染料体系建立、超临界CO2流体染色装备工业放大设计和超临界CO2流体染色工艺放大效应是该项技术产业化应用进程中应着力解决的关键问题。     

分散红73和分散蓝183及其混合物在超临界二氧化碳中溶解度的测定与关联(英文)

The solubility of disperse dyes and their mixture in supercritical carbon dioxide is an important property in study and development of supercritical fluid dyeing technology. In this study, solubilities of C.I. Disperse Red 73, C.I. Disperse Blue 183 and their mixture in supercritical CO2 are measured at temperatures from 343.2 to 383.2 K and pressures from 12 to 28 MPa with a static recirculation method. Under the experimental conditions for the binary (C.I. Disperse Red 73 + CO2 or C.I. Disperse Blue 183 + CO2) and ternary (C.I. Disperse Red 73 + C.I. Disperse Blue 183 + CO2) systems, the solubilities increase with pressure. The solubility of C.I. Disperse Blue 183 decreases with the increase of temperature when the pressure is lower than 16 MPa, and the trend is opposite when the pressure is higher than 16 MPa. However, there is no crossover pressure for C.I. Disperse Red 73. The solubilities are also affected by molecular polarity of dyes. The co-solvent effect exhibited in the dissolving process of mixed dyes promotes their disso-lution in supercritical CO2. The experimental data of solubilities of C.I. Disperse Red 73, C.I. Disperse Blue 183, and their mixture are correlated with the Chrastil model and Mendez-Santiago/Teja model. The former is more accurate.     

Measurement and correlation of solubility of disperse anthraquinone and azo dyes in supercritical carbon dioxide

The solubility of three disperse anthraquinone dyes and two azo dyes in supercritical CO₂ was measured. The tested dyes are Celliton fast blue B, l-amino-2-methylanthraquinone, 1-methylaminoanthraquinone, disperse Red 1 and 4-[4-(phynylazo)phenylazo]-o-cresol. Solubility measurements were made at 313.15-393.15 K and 10-25 MPa in a high-temperature autoclave phase equilibrium apparatus. Pure physical properties of the dyes such as critical constants, molar volumes and vapor pressures were estimated based on semi-empirical methods. Also, the data were quantitatively modeled by both an empirical density correlation and a quantitative equation of state recently proposed by the present authors based on nonrandom lattice theory. We found that anthraquinone disperse dyes in general show higher solubility than azo disperse dyes in supercritical CO₂ within the experimental ranges.     

Solubility of a reactive disperse dye in supercritical carbon dioxide

The solubility of a reactive disperse dye, which was modified from CI Disperse Red 17 with a derivative of 1,3,5‐trichloro‐2,4,6‐triazine as the reactive group, was investigated in supercritical carbon dioxide fluid by employing a batch system equipped with an online spectrophotometer. The investigations were carried out at pressures of 7.5–25.0 MPa, temperatures of 333.15–413.15 K and an equilibrium contact time of 120 min. As revealed from the experimental results, the solubility of the reactive disperse dye increased with pressure in different isotherms, and decreased with temperature. Furthermore, the experimental solubility data were correlated successfully with semi‐empirical models – Chrastil and Del Valle–Aguilera equations, respectively – at various temperatures and pressures.     

Using the solubility parameter to explain disperse dye sorption on polylactide

The solubility parameters of polylactide (PLA), poly(ethylene terephthalate) (PET), and various disperse dyes calculated according to the group contribution method were used to explain the low sorption of some disperse dyes on PLA but the high sorption of the same dyes on PET. It was found that the dyes with high sorption on PLA tended to have solubility parameters near that of PLA, which has a lower solubility parameter than that of PET. It was also found that the solubility parameter, which was calculated based on cohesive energy and molar volume at 25°C, was more appropriate for explaining dyeings at lower temperature, 100 and 110°C, than those at higher temperature, 130°C. Based on the finding that dyes with solubility parameters near that of PLA tend to have high sorption on PLA, general structures for disperse dye that may have high sorption on PLA were proposed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 416–422, 2005     

Solubility prediction of disperse dyes in supercritical carbon dioxide and ethanol as co-solvent using neural network

Nowadays artificial neural networks(ANNs) with strong ability have been applied widely for prediction of nonlinear phenomenon. In this work an optimized ANN with 7 inputs that consist of temperature, pressure, critical temperature, critical pressure, density, molecular weight and acentric factor has been used for solubility prediction of three disperse dyes in supercritical carbon dioxide(SC-CO2) and ethanol as co-solvent. It was shown how a multi-layer perceptron network can be trained to represent the solubility of disperse dyes in SC-CO2. Numeric Sensitivity Analysis and Garson equation were utilized to find out the degree of effectiveness of different input variables on the efficiency of the proposed model. Results showed that our proposed ANN model has correlation coefficient, Nash–Sutcliffe model efficiency coefficient and discrepancy ratio about 0.998, 0.992, and 1.053 respectively.     

Adsorption behaviour of azo disperse dyes on polyurethane fibre

Adsorption isotherms of disperse dyes were measured and the surfaces of dyed polyurethane, cellulose diacetate and polylactic acid fibres were observed using a scanning electron microscope and compared. Obvious crystal growth of the dyes occurred on the surface of the polyurethane fibres. The maximum dye uptake on polyurethane fibres and the degree of crystal growth varied greatly with the dye type. Factors such as the dye affinity for the fibre, crystallisation properties and dye solubility in the dyebath affect the sorbed state of the dye on the fibre surface. A mechanism is proposed for crystal formation on the fibre surface during dyeing of polyurethane fibre with disperse dyes.